Dialkyl Phthalate Plasticizers
Efficiency vs. Molecular Weight and Architecture
The solubility of a plasticizer
in a polymer is governed by
thermodynamic considerations
well documented by numerous
researchers.1,2,3 The effect of
plasticizers on dynamic
properties is less widely known.
This paper tries to gain a better
understanding of the dynamic
mechanical properties as
influenced by differences in
plasticizer molecular weight and
structure.
The majority of plasticizers used for polar
elastomers are organic carboxylic acid esters.
Among this category are dialkyl o-phthalate
esters, a reaction product of a difunctional
phthalic acid, and an alcohol. These plasticizers
are available in both increasing molecular
weight (see Fig. 2) and equivalent molecular
weight (see Fig. 3). Seven plasticizers utilizing
the alcohols listed in Table I were equivalently
compounded at a thirty part (phr)
D.L. HERTZ, JR.
SEALS EASTERN, INC.
RED BANK, NJ 07701
level in the model formula, Table II.
Conventional static and the latest in dynamic
testing were performed to delineate effects of
increasing and equivalent molecular weights.
Experimental
The polar nature of o-phthalate ester
plasticizers is imparted by the –COO– group
identified in Figure 1. The increasing size of the
nonpolar "R" group is a function of the specific
alcohol utilized for the reaction. Since
plasticization is predicated on thermodynamic
miscibility phenomena, the solubility parameter
for each plasticizer was calculated theoretically.
Molar volumes were calculated using Fedors'
group contribution technique." Because of the
polar nature of the molecule, Van Krevelen's
approach' was utilized in order to calculate the
dispersion forces (δd), dipole forces (δp), and
the H-bonding forces (δh), summarized in Table
III.
The alcohols in the esterification reaction
reduce to nonpolar alkyls rather
than polar alkoxy groups, as the alcohol -OH
group condenses with the phthalic acid -H to
give H2O as a byproduct. Thus, the decreasing
solubility parameter value δ is apparent as the
molecular weight of the alcohol increases,
indicating the molecule is becoming less polar.
The fugitive nature of o-phthalate esters needs
no further elaboration so the test conditions
considered were relatively mild, i.e.: 70 hrs. at
100°C. These aging conditions were expected to
show trends toward increasing volatility and
extractability, which they did. The dynamic
mechanical analysis was expected to develop the
relevance of possible relationships between
plasticizers of increasing and equivalent
molecular weights.
Dynamic Mechanical Analysis
The DuPont 982 Dynamic Mechanical
6
Analyzer works on the principle of a forced,
resonant vibratory motion with a preselected
fixed amplitude. The instrument senses the
natural frequency (nf), and supplies additional
energy to compensate for the inherent
elastomeric damping property.
The frequency of oscillation is related to the
modulus of the sample being tested. The low
shear strain amplitude, approximately 0.1
percent at room temperature, gives a higher
"apparent" modulus than what is typically
reported using more conventional test
7
procedures such as ASTM D1043 and 1053 .
Similarly, the higher Tg values are what would
be expected based on deformation (frequency)
8
rate.
The typical stress-strain cycle idealized in
Fig. 4 is reported by the DMA instrument over a
temperature range of -120°C to +20°C. The
elastic stress, E' (tensile storage modulus), is in
phase with the strain, the result of the individual
in Table IV. DIOP had both high elongation and polar δp, and δh components, Table III,
rotational energy barriers in the polymer chain.
the highest tensile stress values at 100, 200 and indicating lesser solubility in the nonpolar
The viscous stress, E" (tensile loss modulus), is
300 percent extension. DBP showed evidence of ASTM # 1 oil.
ninety degrees out of phase with the elastic
being most soluble as indicated by lowest tensile
stress, as viscous resistance depends on rate of
strength and tensile stress at 100 percent. Dynamic Mechanical Analysis
deformation. This resistance is maximum when Tensile Storage Modulus (E' ) or elastic stress
the strain is increasing most rapidly. The for each of the seven samples is shown super
Aging-Air, 70 Hrs. @ 100°C. - The air aging
amplitude of the viscous stress cycle is related to
program was of sufficient duration to indicate imposed in Fig. 5. Fig. 5 is of interest because it
the monomeric friction component. The total grossly illustrates the variation of the glassy
trends of weight loss (see Table IV). Increasing
stress, E* (complex dynamic tensile modulus), modulus strength. The increasing molecular
molecular weight predictably shows decreasing
has an amplitude, Af, equivalent to (A21 + A22)1/2
weight loss. The data-point for DBP of -1.6 weight series of plasticizers (see Fig. 2) have the
The displacement between total stress E* and highest (DEP) and lowest (DBP) E' values. For
percent appears to be out of place and should be
elastic stress E' is the mechanical loss angle δ. equivalent molecular weight plasticizers (see
verified. Durometer change for DOP (+1) is
Tan δ is the loss factor (A2/A1) and is an
surprisingly low compared to other equivalent Fig. 3), which fall within the DBP-DEP limits,
indication of the damping ability. We assumed DOP is low and DIOP is high with a relatively
weight plasticizers (+ 6 to + 8).
tan δ might be influenced by molecular weight narrow spread between. Assuming an interest of
and molecular architecture.
Aging-Oil, 70 Hrs. @ 100°C. - The powerful rubberlike properties, usable data would begin to
extraction effect of ASTM #1 is also well occur at - 40°C.
illustrated in Table IV. The increasing negative Tensile Loss Modulus (E") or viscous stress
Original Properties
volume change for increasing molecular weight is similarly displayed superimposed in Fig. 6.
There were no dramatic original physical
is due to the increasing thermodynamic This is of interest since it illustrates alpha-α,
properties variations as indicated
solubility of the nonpolar ASTM #1 oil with the beta-β , and gamma-γ transitions. Historically,
longer nonpolar alkyl groups (see Fig. 3 and glass transition temperature (Tg) has been
Table III). The methyl, ethyl and butyl mechanically (see Table VI) derived
o-phthalate esters have greater
from Tan δ values. Heijboer9 points out
α-transitions (in most cases, Tg) are main chain
segmental motions. At Tg, it is assumed that
main polymer chains are sufficiently confined
due to reduced space considerations so that
glassy fracture failure can occur. As previously
noted, the α-transitions are the resultant of major
segments of the polymer
chain being frozen in. Heijboer notes two
additional motions occurring with polymers
below their Tg: Local main-chain motion and
side group motion with some cooperation of the
main chain. In Fig. 6 increasing molecular
weight plasticizers, DMP, DEP and DBP, have
α-transitions only. Equivalent molecular
plasticizers have a different response.
DNOP and DCP show strong β -transitions at
-120 and -75°C respectively. DIOP shows both a
β -transition at - 40° and a γ-transition at -88°C.
DOP has only an α- transition at -19°C. The low
E" values at 20°C indicate high resiliency (low
damping) of all seven plasticizers at this
temperature.
Transitions α, β & γ. The very interesting
pattern of low temperature transitions in E", Fig.
6, is worthy of additional investigation. DMP,
DEP, DBP and DOP do not exhibit β or γ
transitions. This could be easily rationalized in
terms of thermodynamic solubility for DMP,
DEP and DBP ("R" equivalent to C1, C2 and C4
chains). DOP, however, is a C6 chain along with
DIOP, which has both a β and γ transition
temperature. Sperati and coworkers10 point out
that polyethylene properties are controlled by
short chain and long chain branching. Their
work notes that an ethyl (C2) branch interrupts
main chain crystallization for about 6-8 carbons
on either side of the ethyl branch. A methyl (C1)
group (DIOP has 2) is not as effective as ethyl.
The β and γ transitions could easily be a
manifestation of Heijboer's description of β and
γ transitions noted earlier. This would be in
agreement with Matsuoka and Kwei's
descriptions11 for the same event.
DNOP and DCP (C2 and C8 chains) appear
to be another case. Apparently the longer chains
are too long to be
thermodynamically soluble and are
mechanically folding back on themselves, thus
creating the β transitions. Alcohols referred to
in Table I and Increasing MW o-Phthalate
Esters, referred to in
Fig. 3 probably give the clues for these various
transitions. The rationalization I leave to those
more knowledgeable in field.
Complex Dynamic Modulus (E*) or total
stress has been calculated by the equation
(E'2 + E" 2)1/2 and is summarized over the
temperature range of -120° to +20°C in Table
V. DBP stands out with relatively flat values
over the range of -10° to +20°C.
Mechanical Loss Angle-Tan β is the ratio of
lost to stored energy. Fig. 7, a superimposition
of DuPont data, is revealing. At -120°, the low
Tan δ values are characteristic of a typical high
modulus linearly elastic solid. This is
understandable by noting the E* values (see
Table V) with modulus ranging from 3.44 GPa
to 5.25 GPa (500,000 to 750,000 psi). Fig. 7,
along with indicating maximum damping
temperature, also illustrates response to Polymers", Elevier Scientific Publishing
increasing temperature. DBP is the quickest to REFERENCES Company, 2nd Edition, p. 152, 183, New
recover rubbery properties while DOP is the York, 1976.
(1) J.H. Hildebrand, R.L. Scott, "Solubility
slowest.
of Non-Electrolytes", Rheinhold
(6a) DuPont 982 Dynamic Mechanical Analysis
Publishing Co. New York, 1950.
System-E42397.
Conclusions (6b) Theory of Operation of the DuPont 982
The predictability of plasticizing events for (2) A. Beerbower, "Advanced Methods for
Dynamic Mechanical Analyzer-F42400.
the methyl, ethyl, and butyl o-phthalate esters Predicting Elastomer-Fluid
has long been well known. The effects of the Interactions", ASLE Paper No. 68
(7) P.B. Lindley, "Engineering Design with
longer chain "R" groups are more complex due LC-21 (1968).
Natural Rubber" MRPRA, 1978, p. 14,
to their nonpolar aspect. This could be a critical Fig. 7.
factor in developing two-phase networks where
the secondary network might be a (3) C. Hansen, A. Beerbower, "Solubility
(8) Ibid, p. 16, Fig. 9.
multifunctional monomer with reactive terminal Parameters", Kirk-Othmer
groups. Encyclopedia, Wiley- Interscience, New
(9) J. Heijboer, "Molecular Origin of
York, 1971, p. 889.
Relaxations in Polymers" in "The Glass
Transition and the Nature of the Glassy
(4) R.F. Fedors, A Method for Estimating
Editor's Note: For readers interested in the State" New York Academy of Science,
Both the Solubility Parameters and
actual DuPont DMA data on which this paper is Vol. 279, p. 104116, New York 1976.
Molar Volumes of Liquids, "Polymer
based, see "Practical Plasticization and
Engineering and Science", February
Plasticizer Theory," Educational Symposium (10) C.A. Sperati, W.A. Franta, H.W.
1974, Volume 14, No. 2, p. 147-154.
No. 10, John H. Starkweather, Jr., "The Effect of Chain
Gifford Library & Information Center, The Branching and Molecular
University of Akron, Akron, OH 44325
(5) D.W. Van Krevelin, "Properties of
 Weight on Physical Properties", J.
Applied Poly. Sci., 75, p. 61276133
(1953).
(11) S. Matsuoka, T.K. Kwei, "Physical
Behavior of Macromolecules" in
"Macromolecules" edited by F.A. Bovey
and F.H. Window, p. 383-392, Academic
Press, New York, 1979.
Presented at the 123rd Meeting of the Rubber
Division American Chemical Society, Toronto,
Ontario, May 11, 1983.
Dr. Phillip B. Gill, E.I. DuPont-Instrument
Group for his invaluable assistance in
developing the dynamic mechanical analysis
data. Dr. Vincent Kuceski, C.P. Hall, for
synthesizing the DNOP sample.
Seals Eastern, Inc.: My associates, H. Bussem
and L. Miller, for the physical testing; and T.
Lamon for her patience in developing charts,
graphs, and tables.